CN101497683A - Preparation of linear bisphenol A phenolic resin - Google Patents
Preparation of linear bisphenol A phenolic resin Download PDFInfo
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- CN101497683A CN101497683A CNA2008100306191A CN200810030619A CN101497683A CN 101497683 A CN101497683 A CN 101497683A CN A2008100306191 A CNA2008100306191 A CN A2008100306191A CN 200810030619 A CN200810030619 A CN 200810030619A CN 101497683 A CN101497683 A CN 101497683A
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- phenolic resin
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Abstract
The invention provides a preparation method of bisphenol A novolac phenolic resin, which comprises the following steps: bisphenol A is added in solvent with the weight being 25-100 percent of the weight of the bisphenol A, acidic catalyst with the weight being 0.7 to 2 percent of the weight of the bisphenol A, formaldehyde is continuously added at the temperature of 70-110 DEG C for 0.25-2.5 hours, all reactants react for 1-10 hour(s) at the temperature of 70-110 DEG C, and the reactants are heated and depressurized to remove the solvent, thus the bisphenol A novolac phenolic resin is obtained, wherein the mol ratio of formaldehyde and the bisphenol A is 0.3:1 to 3:1. The prepared bisphenol A novolac phenolic resin has the residual quantity of the bisphenol A of smaller than 15 percent, the softening temperature of 100-125 DEG C, and the dissolution iscosity of 63-67 percent of butanone solvent at 25 DEG C of 4000-6000 Pa.s. The invention has excellent physical property under the condition that the molecular weight is kept higher.
Description
Technical field
The present invention relates to a kind of preparation method of linear bisphenol A phenolic resin.
Background technology
Along with the development of industrial technology, the demand of the substrate of printed circuit board (PCB)---copper-coated laminate is increasing severely, and its main application has: data processing equipment (computer etc.), automatic control device, communication apparatus and household electrical appliance etc.Needs for the multifunction that adapts to these apparatuses, light, thin, short and smallization, copper-coated laminate is faced with graph thinning, through hole miniaturization and the gap of wiring mode and reduces the test that causes densification, miniaturization of components and process automation, element installation automatization, and its electric property, mechanical property, processing characteristics all will further improve.For adapting to the needs of densification, material as veneer sheet is also required not take place in the processing of loop and under the thermal shocking (scolder adjustment, scolding tin impregnating) after the processing defectives such as hickie, factors such as the second-order transition temperature of epoxy-resin systems and cross-linking density have a significant impact the generation of stain, the generation that can cause stain of adhering to of the softening and powder of resin.We can say that all material properties that worsen because of being heated all can cause the generation of stain.So the thermotolerance that improves copper clad plate just needs to improve the resistance toheat of used Resins, epoxy oligopolymer and solidifying agent, and the improvement important influence of solidifying agent wherein.Present main flow solidifying agent is a Dyhard RU 100 in the processing and manufacturing of epoxy resin veneer sheet, however the veneer sheet second-order transition temperature (Tg) that obtains therefrom lower (less than 120 ℃), water tolerance is relatively poor, and every performance range of decrease is bigger under the high temperature.
There is the investigator to propose to use multi-functional phenol resol to replace the solidifying agent of Dyhard RU 100 as epoxy copper-clad laminate panel material, Japanese Patent JP61072018 reports this, but deep development along with the research application, the deficiency of linear phenolic resin solidifying agent also just exposes to the open air out, the existence that mainly shows as free phenol in the solidifying agent resol can cause the goods intrinsic colour darker, and the problem that the cured article color and luster is further deepened usually takes place under the heating process condition of the course of processing, the free phenol of simultaneously even more serious is single functionality also causes the decline of cured article over-all properties, affects greatly for the printed-wiring board (PWB) inner quality.In the resol building-up process of this patent report, because the phenolic aldehyde mol ratio is bigger, phenol can't react completely, and residual free-phenol surpasses 20% in the resol.
Dihydroxyphenyl propane has two reactive functionality phenolic hydroxyl structures in aldehydes matter, and good stability, therefore if substitute the phenol of simple function group with dihydroxyphenyl propane in resol synthetic, the resin product that obtains should be to overcome the deficiency that general resol is made the solidifying agent of epoxy copper-coated laminate.Linear bisphenol A phenolic resin synthetic resin look shallow is and stable simultaneously, can variable color when being heating and curing.In the prior art, only having reported a kind of refractory ring oxygen complex that is used for deflector coil at patent JP5820082 has used linear bisphenol A phenolic resin as an one important component; Patent Cs229037 has reported the coated material that is used for the protection of the bonding or glass processing front surface of glass surface and has adopted the linear phenolic aldehyde of dihydroxyphenyl propane to make solidifying agent to improve the water proof and wearable performance.Linear bisphenol A phenolic resin is not reported as epoxy copper-coated laminate solidifying agent.In above two patents, all the method that reduces the residual dihydroxyphenyl propane of bisphenol A phenolic resin is not reported.
Summary of the invention
The invention provides a kind of preparation method of linear bisphenol A phenolic resin, improved the transformation efficiency of dihydroxyphenyl propane, the residual quantity of dihydroxyphenyl propane in resin is reduced to below 15%, when cured epoxy resin, do not have the phenomenon that the small molecules dihydroxyphenyl propane is separated out.Improve resin crosslinks density simultaneously,, particularly improve thermotolerance and wet fastness to improve the performance of cured article.
Concrete steps of the present invention are: dihydroxyphenyl propane is added in the solvent of own wt 25%～100%, the an acidic catalyst that adds dihydroxyphenyl propane quality 0.7%～2%, add phenolic molar ratio continuously than being the formaldehyde of 0.3:1～3:1 at 70～110 ℃, the reinforced time was controlled at 0.25 hour～2.5 hours, again under 70～110 ℃, reacted 1～10 hour, the decompression that heats up removes solvent, gets linear bisphenol A phenolic resin.
The solvent that uses in the above-mentioned synthetic method can be the lower alcohols solvent: methyl alcohol, ethanol, Virahol, propyl carbinol, primary isoamyl alcohol; Ketones solvent: ketone, butanone, methyl iso-butyl ketone (MIBK); Aromatic hydrocarbon solvent: toluene, dimethylbenzene etc.; One or more mixtures in ether solvent: diox, the diisopropyl ether with arbitrary proportion.
An acidic catalyst that uses in the above-mentioned synthetic method can be a mineral acid: phosphoric acid, hydrochloric acid, sulfuric acid, nitric acid; Organic acid: formic acid, acetate, oxalic acid, Whitfield's ointment, toluenesulphonic acids; Lewis acid: one or more in boron trifluoride, alchlor, the tin chloride are with the mixture of arbitrary proportion.
The formaldehyde that uses in the above-mentioned synthetic method can be formalin solution, trioxymethylene or Paraformaldehyde 96.
In implementing process of the present invention, the usage quantity of solvent is 25%～100% of a dihydroxyphenyl propane, and the ideal consumption is 30%～70%.When quantity of solvent less than 25% the time, reaction system concentration is higher, speed of response is too fast, reaction has the danger that gel takes place; When quantity of solvent greater than 100% the time, reaction system concentration is on the low side, speed of response is slow, the molecular resin amount is on the low side, the dihydroxyphenyl propane residual quantity is higher.
Catalyst levels is 0.7%～2% of a dihydroxyphenyl propane quality, and when catalyst levels was higher than 2%, speed of response was too fast, and molecular weight is higher, and resin viscosity increases; When catalyst levels less than 0.7% the time, speed of response is slower, molecular weight is on the low side, the dihydroxyphenyl propane residual quantity is higher.
The mol ratio of formaldehyde and dihydroxyphenyl propane is 0.3:1～3:1, when the mol ratio of formaldehyde and dihydroxyphenyl propane〉3 the time, the molecular resin amount is higher, and reaction has the danger that gel takes place; When the mol ratio of formaldehyde and dihydroxyphenyl propane＜0.3, the intact content of bisphenol A of unreacted is higher in the resin, and molecular-weight average is low excessively, and during cured epoxy resin, cross-linking density descends, and condensate performance, especially thermotolerance and wet fastness descend.
Compared with prior art, the present invention has following tangible advantage:
1. the solubility promoter that uses of the present invention can promote reaction to carry out well, and the dihydroxyphenyl propane residual quantity in the resin is less than 15%, so the phenomenon that dihydroxyphenyl propane is separated out can not take place during cured resin, can not cause that the cured article color and luster deepens.
2. the softening temperature of the bisphenol A phenolic resin of the present invention's manufacturing is 100～125 ℃, and dissolving viscosity (65 ± 2% butanone solutions, 25 ℃) is 5000 ± 1000mPa.s, is keeping making it have good physicals under the molecular weight condition with higher.
Embodiment
Embodiment 1
In the four-hole boiling flask that prolong, thermometer, agitator are housed, add dihydroxyphenyl propane 200g, propyl carbinol 20g, butanone 44g, heating up to stir fully dissolves reactant, adds oxalic acid 2g, adds Paraformaldehyde 96 20g 4 times at 90 ℃ of branches, each 5g added in 30 minutes, was warming up to 95 ℃ and kept reaction 4 hours.The decompression desolventizing that heats up then, temperature reaches 200 ℃, pressure reaches-removal pressure during 0.1Mpa, pours out product, linear bisphenol A phenolic resin.
Embodiment 2～12
Working method is identical with embodiment 1, and reaction conditions and product the results are shown in following table.
Table 1 reaction conditions
| Embodiment | F/P | Solvent species and consumption % | Catalyst type and consumption % | Formaldehyde adds temperature ℃ | Formaldehyde joining day h | Holding temperature ℃ | H holds time |
| 1 | 0.76 | Propyl carbinol 10%, butanone 22% | Oxalic acid 1% | 90 | 0.5 | 95 | 4 |
| 2 | 0.3 | Toluene 40% | Toluenesulphonic acids 0.5%, acetate 0.2% | 95 | 0.25 | 105 | 1 |
| 3 | 1.2 | Virahol 15%, diisopropyl ether 10% | Oxalic acid 0.7%, boron trifluoride 0.7% | 70 | 1 | 70 | 3 |
| 4 | 2.4 | Methyl alcohol 30% ， diox 50% | Alchlor 1%, phosphoric acid 0.8% | 105 | 2 | 110 | 6 |
| 5 | 1.75 | Ethanol 25%, dimethylbenzene 15% | Hydrochloric acid 0.15%, toluenesulphonic acids 1% | 75 | 0.75 | 80 | 4 |
| Embodiment | F/P | Solvent species and consumption % | Catalyst type and consumption % | Formaldehyde adds temperature ℃ | Formaldehyde joining day h | Holding temperature ℃ | H holds time |
| 6 | 1 | Ketone 10%, propyl carbinol 28% | Formic acid 0.6%, alchlor 0.25% | 85 | 1 | 85 | 4 |
| 7 | 2.85 | Primary isoamyl alcohol 32%, toluene 60% | Whitfield's ointment 1.1% | 110 | 2 | 95 | 7 |
| 8 | 0.55 | Methyl iso-butyl ketone (MIBK) 15% ， diox 13% | Sulfuric acid 0.1%, tin chloride 0.8% | 75 | 0.5 | 80 | 2 |
| 9 | 1.4 | Diox 85% | Formic acid 1.3% | 100 | 1 | 90 | 4.5 |
| 10 | 2.15 | Virahol 45%, ketone 40% | Acetate 1%, boron trifluoride 1% | 90 | 1.5 | 95 | 6.5 |
| 11 | 3 | Propyl carbinol 75%, toluene 25% | Phosphatase 11 .75% | 85 | 2.5 | 95 | 10 |
| 12 | 1.05 | Diisopropyl ether 30% | Toluenesulphonic acids 0.5%, oxalic acid 03% | 90 | 1.5 | 95 | 3 |
Annotate: the percentage ratio that solvent load is pressed dihydroxyphenyl propane weight calculates.
Table 2 product result
| Embodiment | Softening temperature ℃ | Dissolving viscosity mPa.s (65 ± 2%MEK solution) | BPA residual quantity % |
| 1 | 101 | 5410 | 12.86 |
| 2 | 114 | 4890 | 14.33 |
| 3 | 112 | 5015 | 11.98 |
| 4 | 106 | 4900 | 13.79 |
| 5 | 121 | 5520 | 14.56 |
| 6 | 123 | 4650 | 12.26 |
| 7 | 107 | 5735 | 11.71 |
| 8 | 110 | 5200 | 13.20 |
| 9 | 111 | 4650 | 14.80 |
| 10 | 108 | 5g00 | 13.65 |
| 11 | 118 | 4375 | 14.12 |
| 12 | 109 | 5785 | 11.30 |
Claims (4)
1, a kind of preparation method of linear bisphenol A phenolic resin, it is characterized in that dihydroxyphenyl propane is added in the solvent of own wt 25%～100%, the an acidic catalyst that adds dihydroxyphenyl propane quality 0.7%～2%, add phenolic molar ratio continuously than being the formaldehyde of 0.3:1～3:1 at 70～110 ℃, the reinforced time was controlled at 0.25 hour～2.5 hours, under 70～110 ℃, reacted 1～10 hour again, the decompression that heats up removes solvent, gets linear bisphenol A phenolic resin.
2, method according to claim 1 is characterized in that the solvent that uses can be the lower alcohols solvent: methyl alcohol, ethanol, Virahol, propyl carbinol, primary isoamyl alcohol; Ketones solvent: ketone, butanone, methyl iso-butyl ketone (MIBK); Aromatic hydrocarbon solvent: toluene, dimethylbenzene etc.; One or more mixtures in ether solvent: diox, the diisopropyl ether with arbitrary proportion.
3, method according to claim 1 and 2 is characterized in that an acidic catalyst that uses can be a mineral acid: phosphoric acid, hydrochloric acid, sulfuric acid, nitric acid; Organic acid: formic acid, acetate, oxalic acid, Whitfield's ointment, toluenesulphonic acids; Lewis acid: one or more in boron trifluoride, alchlor, the tin chloride are with the mixture of arbitrary proportion.
4, method according to claim 1 and 2 is characterized in that the formaldehyde that uses can be formalin solution, trioxymethylene or Paraformaldehyde 96.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100306191A CN101497683A (en) | 2008-02-02 | 2008-02-02 | Preparation of linear bisphenol A phenolic resin |
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|---|---|---|---|
| CNA2008100306191A CN101497683A (en) | 2008-02-02 | 2008-02-02 | Preparation of linear bisphenol A phenolic resin |
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| CN101497683A true CN101497683A (en) | 2009-08-05 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102127198A (en) * | 2011-01-13 | 2011-07-20 | 宁波卡利特新材料有限公司 | Method for preparing bisphenol A type boron phenolic resin |
| CN103601401A (en) * | 2013-11-25 | 2014-02-26 | 金陵科技学院 | Preparation method of sulfonated bisphenol A-formaldehyde condensate superplasticizer |
| CN103626941A (en) * | 2013-11-01 | 2014-03-12 | 南通星辰合成材料有限公司 | Bisphenol a modified phenolic resin and preparation method thereof |
| CN105669925A (en) * | 2016-02-24 | 2016-06-15 | 无锡旺绿鸿纺织品有限公司 | Preparation method of phenolic resin for manufacturing polishing cloth |
| CN108948299A (en) * | 2018-08-17 | 2018-12-07 | 陕西科技大学 | A kind of bisphenol A formaldehyde phenolic resin and its synthetic method |
| CN113912801A (en) * | 2021-11-25 | 2022-01-11 | 浙江自立高分子化工材料有限公司 | Anhydrous phenolic resin binder for magnesia-calcium brick and preparation method thereof |
| CN114478427A (en) * | 2022-02-18 | 2022-05-13 | 四川金象赛瑞化工股份有限公司 | High-performance thermosetting resin curing agent/diluent and preparation method thereof |
-
2008
- 2008-02-02 CN CNA2008100306191A patent/CN101497683A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102127198A (en) * | 2011-01-13 | 2011-07-20 | 宁波卡利特新材料有限公司 | Method for preparing bisphenol A type boron phenolic resin |
| CN103626941A (en) * | 2013-11-01 | 2014-03-12 | 南通星辰合成材料有限公司 | Bisphenol a modified phenolic resin and preparation method thereof |
| CN105017714A (en) * | 2013-11-01 | 2015-11-04 | 南通星辰合成材料有限公司 | Preparation method of bisphenol A modified phenolic resin |
| CN103626941B (en) * | 2013-11-01 | 2016-01-20 | 南通星辰合成材料有限公司 | Bisphenol a modified phenolic resin and preparation method thereof |
| CN105017714B (en) * | 2013-11-01 | 2017-11-24 | 南通星辰合成材料有限公司 | The preparation method of bisphenol A modified phenolic resin |
| CN103601401A (en) * | 2013-11-25 | 2014-02-26 | 金陵科技学院 | Preparation method of sulfonated bisphenol A-formaldehyde condensate superplasticizer |
| CN103601401B (en) * | 2013-11-25 | 2015-07-15 | 金陵科技学院 | Preparation method of sulfonated bisphenol A-formaldehyde condensate superplasticizer |
| CN105669925A (en) * | 2016-02-24 | 2016-06-15 | 无锡旺绿鸿纺织品有限公司 | Preparation method of phenolic resin for manufacturing polishing cloth |
| CN108948299A (en) * | 2018-08-17 | 2018-12-07 | 陕西科技大学 | A kind of bisphenol A formaldehyde phenolic resin and its synthetic method |
| CN113912801A (en) * | 2021-11-25 | 2022-01-11 | 浙江自立高分子化工材料有限公司 | Anhydrous phenolic resin binder for magnesia-calcium brick and preparation method thereof |
| CN113912801B (en) * | 2021-11-25 | 2023-08-22 | 浙江自立高分子化工材料有限公司 | Anhydrous phenolic resin binder for magnesia-calcium bricks and preparation method thereof |
| CN114478427A (en) * | 2022-02-18 | 2022-05-13 | 四川金象赛瑞化工股份有限公司 | High-performance thermosetting resin curing agent/diluent and preparation method thereof |
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Open date: 20090805 |